Novel reactions of perfluoroalkylphenyl sulfides with organolithium reagents

Good Partnership between Sulfur and Fluorine: Sulfur-Based Fluorination and Fluoroalkylation Reagents for Organic Synthesis

“…Trifluoromethyl phenyl sulfide (PhSCF 3 , 27 ) is a stable compound that can be easily prepared either from PhSCH 3 via α-trichlorination followed by a halogen-exchange reaction, or from PhSSPh via trifluoromethylation with fluoroform . Although reductive lithiation can activate the C–S bond of nonfluorinated sulfides to generate alkyllithiums for various transformations, it is not applicable for trifluoromethylation due to the notoriously low stability of CF 3 Li . In addition, the sulfur atom in a sulfide is less electrophilic toward the common anionic species such as alkoxides than that in a sulfoxide or sulfone, thus the activation of the CF 3 –S bond in a sulfide 27 for nucleophilic trifluoromethylation is far from trivial.…”

Synthetic Methods for Compounds Having CF3–S Units on Carbon by Trifluoromethylation, Trifluoromethylthiolation, Triflylation, and Related Reactions

“…The conversion of aryl halides to aryl trifluoromethyl sulfides has been widely investigated. Trifluoromethylthiocopper (CuSCF 3 ) was the first convenient reagent for reactions with aryl halides (eq a, Scheme ). − Alternatively, CuSCF 3 could be formed in situ from Hg­(SCF 3 ) 2 /Cu and the condensation product was obtained in comparable yield (eq b, Scheme ). , In order to improve yields and the purification of products, other versions of the copper salt were also developed (eqs c and d, Scheme ). , Recently, the Weng group developed a ligated copper trifluoromethylthiolate species [(bpy)­CuSCF 3 ] as an efficient reagent for the trifluoromethanesulfenylation of aryl halides (eq e, Scheme ) …”

[(bpy)CuSCF3]: A Practical and Efficient Reagent for the Construction of C–SCF3 Bonds

“…1960s. Many nucleophilic reagents have been reported for the effective construction of C-SCF 3 bonds, such as Hg(SCF 3 ), 37 Ag(SCF 3 ), 38 Cu(SCF 3 ) 39 and Cs(SCF 3 ). 40 However, there are some limitations in the synthesis of these reagents, such as the use of highly toxic and expensive materials or the requirement for additional transition metal as the catalyst in the reaction.…”